Hydroxy sulphonated fatty acid esters and their production



. June 25 1935 PATENT OFFICE j 'HYDBOXY SULPHONATED FA'l'l'Y ACIDES'I'EBS AND THEIR PRODUCTION Charles 0. Clark. St. Bernard,ohimassignor to The Procter d; Gamble Company, Cincinnati,

Ohio, a corporation of Ohio No Drawing. Application July s. 1033, Seriala No. 619,217 7 V momma. (cl. zoo-10c) This invention relates to newfoaming, emulsifying, wetting and cleansing agents comprising substanceshaving the general molecular structure of derivatives of glycerol inwhich one of the .hydroxyls is esterifled with a higher may acid.

one remains unchanged, and the third is replaced by the 80:1!group,'where M may be a-metal or other basic radical. Such compounds mayalso be considered as salts of sulphonated monoglycerides of fattyacids.

The objects of the invention are to provide new and useful compoundshaving the desirable properties abovementioned, and to provide means forproducing same.

Itis known that foaming, emulsifyin wetting and cleansing properties arepossessed by sulphate esters of certain. oils, fats, waxes, fatty acidsand fatty alcohols, and that such properties are also possessed by thesalts of certain sulphonic acids, such, for example, as those whichcanbepreparedbyestcrlfyingthealkalimetal salts of isetliionic acid withfatty acids. It is also known that 'compoundawith similar properties canbe prepared by combining such products as the sodium salt of 1,2-hydroxypropane sulphonic acid, or thesodium salt of 1,3-hydroxypropanesulphonic acid with fatty acids or fatty acid chlorides. I makeno claim to such com-' poimds, which do not contain a free hydroxylgroup in the. nucleus of the molecule.

I havefoimd that a new class of compoundsmf different structure from theabove, but possessing the above-mentioned desirable properties to aremarkable degree, can be prepared by causing salts of glycerolalpha-sulphonic acid to react with a higher saturated or unsaturatedfatty acid or fatty acid halide, thereby obtaining the mono-fatty acidester. or a mixture of the monoand the div-fatty acidesters, of the saidsalts of.

glycerol alpha-sulphonic acid. I have also fund that the mono-fatty acidester of an alpha-glycerol sulphonate, possessing a free hydroxyl grouplathe-nucleus of the molecule, has the desirable foaming, emulsifyinwetting, cleansing and dispersing properties to agrea'ter extent thanhas the di-fatty acid ester or a mixture of the monoand the di-fattyacid esters, and that a separation of the relativelymore desirablemono-fatty acid ester from the relatively less desirable difatty acidester can be eifected by washing with,

'orfipreferably by crystallization from ethyl alcohol or otherlow-boiling alcohol. Such separation is sometimes desirable, but is notin all cases essential, and my invention is not limited tothe purifiedproduct obtained by such separation.

ized by a molecular nucleus of three carbon T atoms, to one of whicha'free hydroxyl group is attached, to another of which ahigher fattyacid radical is attached by an ester linkage, and to the third of whichthe salt of a sulphonic acid group, 803M, is attached, the sulphurof-this last mentioned group being combined directly with the terminalcarbon atom of the said nucleus; The product so obtained is of thegeneral formula: XCHzCHYCHaSOaM, where M may be any alkali metal,alkaline earth metal, heavy metal, ammonium or basic organic radicalwhich, in the above combination, is soluble in water, and where X may bea fatty acid radical, in which case Y is a hydroxyl group, or else X maybe'a'hydroxyl group in which case Y is a fatty acid radical. The alkalimetals and magnesium form especially useful products, but it should beunderstood that any metal or basic radical that forms water-solublecompounds may also be used. The fatty acid radical in either case may beany set-- urated or unsaturated fatty acid radical having six or morecarbon atoms in the molecule. Products of this type differ frompreviously used fatty acid esters of sulphonic acids in that theypossess an alcoholic hydroxyl group in the nucleus of the been found toadd greatly to the solubility of the compound in water and to render itespecially useful in hard waters. Thus the replacement of thishydroxylgroup by hydrogen or by a higher. fattyacid group lessens thefoaming emulsifying, wetting and cleansing power of the product and itssolubility in hard waters. r.

. It is understood that in making the products of my invention, in placeof aflsingle fatty acid a mixture of fatty acids may be'used, such forexa'mpleas occurs in any of the natural fats or oils; likewise a mixtureof or basic radicals may-housed in place of a single one. The fatty,acids from 'cocoanutoil or' palm. kernel oil are' es'pecially suitableproducts;

The products'of my invention be made by means of severaldifferentfreactlons depending on the nature of the materials. One methodis to start with asolublesalt, such for example as the sodium saltgofglycerol sulphonic acid (sodium 'LZ-dihydroxy' propane-3-suipho-' nate,prepared by alpha' clilorohydrin with aqueous NazSO: solution ahdsuhsequent removal o'fwater)v and cause itto combine withthe desiredfatty acids. This is by heating one molecular proportion of theaim-ementioned salt with one molecular proportion of the fatty acid in asuitable reacting chamber equipped with a reflux condenser. For thebest. yields, the mixture must be heated with stirring to a temperatureranging from about 150 to 225 C. for a period of about 5 to 10 hours.

The water formed in the reaction is allowed to escape while any fattyacids which volatilize are returned to the reacting chamber by thereflux condenser.

A second method is to start with the same form of salt of glycerolsulphonic acid and heat same with a fatty acid chloride instead of afatty acid itself. In this case again, equal molecular quantitles areused and the process is similar except that it proceeds at a much lowertemperature, such as from approximately 75 to 125 C., for a period ofabout '5 to 10 hours. The hydro- .chloric acid formed in the reaction isallowed to escape, but any acidity still remaining at the end of thereaction should be neutralized with caustic soda or other basic reagent.

' A third method is to start with a soluble salt,

such for example as the sodium salt, of l-chloro- 2-hydroxypropane-3-sulphonic acid and heat same as above with an alkali soap of afatty acid. In this case, a temperature of about 100 to 200 C. isrequired with stirring for about 5 to 10 hours.

All three of these methods will yield products of the same chemicalstructure and properties, differing only in the nature and amount of theimpurities which may be present as a result of the method used. Thefirst and second methcds, for example, may result in the presence, asimpurities, of fatty acids or of the sodium salt of glycerol sulphonicacid, while the second and third methods may result in the presence, asimpurities, of alkali metal soap or of sodium chloride besidesunacted-on materials. In the case of the third method, there may also bepresent unreacted sodium salt of 1-chioro-2-hydroxy propane-3-sulphonicacid. The reaction products may in all cases be purified suflicientlyfor practical purposes by washing with cold ethyl alcohol or otherlow-boiling alcohol, or preferably by dissolving in hot ethyl alcohol,filtering to remove insoluble salts and other matters, and crystallizingfrom the alcoholic solution. The product thus obtained will consistessentially of the mono-fatty acid ester, substantially free from thedi-fatty acid ester, and containing variable amounts of other impurities(such as the abovementioned sodium chloride, sodium 1,2-dihydroxypropane- 3-su1phonate, or sodium i-chloro- 2- hydroxypropane-3-sulphonate) depending upon the thoroughness of thepurification treatment to which it is subjected. The purified product isa dry powder nearly white in color, stable under all ordinaryconditions, and possessing in aqueous solution extraordinary foaming,emulsifying, wetting and cleansing properties, showing these propertiesstrongly even in hard water.

The following examples will illustrate different methods of making theproducts of my invention, all quantities being by weight.

Example 1 180 parts of the sodium salt of glycerol sulphonic acid(sodium 1,2*dihydroxy propane-3-sulphopate, prepared by heating alphachlorohydrin with aqueous NazSOs solution and subsequent removal ofwater) are heated at 150 to 225 C. for 6 hours with stirring with 210parts of the fatty acids from cocoanut oil, the water evolved in tliereaction being allowed toescape and the fatty acids being returned tothe reacting chamber by suitable reflux condensation. The product ofthis reaction is then purified by washing with cold ethyl alcohol orother low-boiling alcohol, or preferably by dissolving in hot ethylalcohol, filtering to remove insoluble inorganic salts. or otherinsoluble matter and crystallizing from the alcoholic solution. Theproduct thus obtained is a nearly white dry powder, stable underordinary conditions of use, and possessing in aqueous solutionextraordinary foaming, emulsifying, wetting and cleansing properties andcan be used advantageously even in hard water.

Example 2 195 parts of the potassium salt of 1,2-dihydroxypropane-3-sulphonic acid are heated at 75 to 125 C. with stirring, for10 hours with 300 parts of oleic acid chloride. The produce of thereaction is made neutral with NaOH, NazCOa, NH: or other suitable alkaliand is then purified as in Example '1. erties described under Example 1.

Example 3 200 parts of the sodium salt of l-chloro-2- hydroxypropane-3-sulphonic acid are heated at to 200 C. with stirring for 5hours with 300 parts of sodium soap prepared from tallow. The product ofthe reaction may then be purified as in Example 1, and it then possessesthe properties described in Example 1.

Example 4v The triethanolammonium (sometimes called triethanolamine)compound may be formed as follows:

290 parts of the sodium salt of commercial stearic acid are heated atabout C., with stirring for 4 hours with 325 parts of thetriethanolammonium salt of 1-chloro-2-hydroxy propane-3-sulphonic acid(prepared by heating 1,3dichlorohydrin with triethanolamminiumsulphite). The product of the reaction may be purified as in Example 1,and then possesses the properties described in Example 1;

Having thus described my invention, whatI claim as new and desired tosecure by letters Patent is:

1. A new composition of matter consisting of monohydric'aliphatic'alcohols derived from a soluble salt of 1,2-dihvdroxypropane-fii-sulphonic acid by e'sterification of one of its hydroxylgroups with a fatty acid containing at least six carbon atoms.

2. The process of preparing foaming, emulsifying, wetting and cleansingagents comprising chemically combining one molecular weight of a solublesalt of 1,2-dihydroxy propane-3-sulphonic acid with one molecular weightof a fatty acid having at least 6 carbon atoms;

3. The process of preparing foaming, emulsifying, wetting and cleansingagents comprising chemically combining one molecular weight of 1halogen-2-hydroxy propane-3-sulphonic acid with one molecular weight ofthe alkali metal soap of afatty acid having at least six carbon atoms.

4. Wetting, cleansing and emulsifying agents consisting of compounds ofthe general formula CHzXCHXCHzSOsM The purified product has thepropwhere M may be an equivalent weight of any alkali metal, alkalineearth metal, heavy ammonium or basic organic radical which, in the abovecombination, is soluble in water and where one X is a hydroxyl group andthe other x con- 'sistsofthe groupRCOQinwhichRistheaibl radical'of afatty acid having at least six carbon atoms.

A new composition of matter consisting of compounds of the generalformula CHaXCHXCHaSOaM where M maybe an equivalent weight of any alkalimetal, alkaline earth metal, heavy metal,

' ammonium or basic organic radical which in the above combination issoluble in water and where one x is a hydroxyl group and the other xconsists of the group RG00, in which it re wts alkyl radicals oi. fattyacids derived from c ut oil. 7

6. The process which comprises causing a compound selected'from thegroup consisting of 1,2-dihydroxy propane fl-sulphonic acid, 1halogen-2-hydroxy propane-3-sulphonic acid, and

the soluble salts of these compounds, to react with a compound selectedfrom the group consisting of fatty acids containing at least six carbonatoms per molecule, and their alkali metal salts.

7. The process which comprises causing a compound of the general formulanocmcnoncmsom wherein M stands for an equivalent weight of any alkalimetal, alkaline earth metal, heavy metal, ammonium or basic organicradical which in the above combination is soluble in water, to reactwith a fatty acid whose molecule contains at least six carbon atoms.

. 8; The process which comprises causing a com-- pound of the generalformula i XCHsCHOHCHaSOsH.

a,ooe,soo

metal,

wherein 2 stands for a halogen atom and M stands for an equivalentweight of any alkali metal, alkalineearth metal, heavy metal, am-

monium or basic organic radical which in the.

above combination is soluble in water, to react with an alkali metalsalt of a fatty acid whose molecule contains at least six; carbon atoms.

9. Wetting, cleansingand emulsifying agents consisting of the productsformed by causing a compound of the general formula HOCHsC'HOHCHaSOaMwherein M stands for an equivalent weight of- XCHsCHOHCHrSOsM wherein Xstands for a halogen atom and M stands for an equivalent weight ofv anyalkali metal, alkaline earth metal, heavy metal, ammonium or basicorganic radical which in the above combination is soluble in water, toreact with an alkali metal salt of a fatty acid whose molecule containsat least six carbon atoms, said products of reaction great power towater and in soft water;

CHARLES C. CLARK.

I DI SCI-Al M E R 2,006,309.0I|q1-ls 0'. Clark, St. Bernard, Ohio.Hrnnoxr Sunrno'rurnn Fury Acm ddsrnas m Tnmn PRODUCTION. Patent datedJune 25, 1935.

V 1 Disclaimer filed DecemberIS, 1935, by the assignee, The Procter d:Gambk Hereby enters this disclaimerto the process of claim 6 insofar assuch comprises causing l 2 profpane 3-sulfon ic acid to react with acompound ected from the group consisting-of atty acidscontaim'ng atleast six carbon atoms per molecul'e'and their alkah'metal sal ts, andin so far as such process comprises causing the soluble salts of 1 :2dihydroxy ropane 3 sulphonic acid to react with con [Qflicml GasefleJanuary 14, 1986.]

e lk limeal tsofthe fft at least six carbon toms per molecule. v m o "dfoam,-emulsify, wet, and cleanse, both in hard DISCLAIMER2,006,309.0Iwrles 0. am, St. Bernard, Ohio. Hrnnoxr SULrnoNa'mn FATTYAcm -Esmns m Tlmm PRODUCTION. Patent dated June 25, 1935. gisclaimerfiled December 18 1935, by the assignee 17w Procter (f: Gamble Herebyenters this disclaimer to the process of claim 6 in so far as suchprocess comprises causing 1 :2 dihydroxy pro 0 3-sulfonic acid to reactwith a compound selected from the group consisting of atty acidscontaining at least six carbon atoms per molecule'and their alkali metalsalts, and in so far as such process comprises causing the soluble saltsof 1 2 dihydroxy ropane 3 sulphonic acid to react with a compoundselected from the alkali metal ts of the group consisting of fatty acidscontaining at least six carbon atoms per molecule.

[Qflicull January 14, 1936.]

